DE69907229T2 - FLAMMABILITY INJECTOR FOR POLYMER MATERIAL - Google Patents

Abstract

The present invention relates to a combustion retardant for polymeric materials that consists of a new complex compound comprising an ammonia salt of alkylphosphonic acid amide as well as ammonium chloride. This invention also relates to methods for producing various polymeric materials using this combustion retardant.

Description

Technical field

The invention relates to a technique for the production of polymer compositions based on carbon chain polymers (Polyethylene, polypropylene, polystyrene, synthetic rubbers and copolymers various compositions), hetero chain polymers (polyester, Epoxy and phenolic resins) and composite materials of various compositions and fillings with low flammability, low toxicity of those emitted during combustion Gases and low flue gas development.

Polymer materials are widely used Application in the cable and motor industry, in electrical consumer goods, in Construction, in other consumer goods, in the gas and oil production industry, in Aerospace technology and for the production of packaging materials.

State of the art

The majority are technically manufactured A major problem with materials is their flammability and high burn rate from the emission of a large amount toxic products is accompanied.

To reduce flammability carbon chain polymers come physical (Kistelman V.I., Physical Methods of Modifying Polymer Materials, Moscow, Khimiya, 1980, p. 223) and chemical modification methods as well as a combination thereof for use, e.g. B. photochemical modification (Kachan A.A., Zamotayev P.V., The Photochemical Modification of Polyolefins, Kiev, Naukova Dumka, 1990, 5, 276). The chemical modification leads by halogenation to a stronger one Flammability reduction. To use this method to make a polyolefin To get rid of the external heat source, you have to polyethylene (PE) and polypropylene (PP) up to a halogen content of 25 to 40% by weight chlorination (Aseyeva R.M., Zaikov G. Ye., The Combustion of Polymer Materials, Moscow, Nauka, 1991, p. 150). With such a Chlorine content is the crystallinity of PE and PP are drastically reduced so that they are made of thermoplastics Elastomers are converted (Sirota A.G., Modification of the Structure and Properties of Polyolefins, Moscow, Khimiya, 1984, P. 150). Chlorinated PE is used as a flame-retardant material in itself and as a polymeric flame retardant for other polymer materials. The The main problems with chlorinated polyolefins are that they are a low heat resistance and emit toxic products, which limits their use.

Polymers with higher heat resistance and higher oxygen index (OI) (about 27%) can be obtained by sulfochlorination (Aseyeva R.M., Zaikov G. Ye., The Combustion of Polymer Materials, Moscow, Nauka, 1991, P. 150). Sulfochlorination can be like chlorination to form of elastomers.

(N.B. The oxygen index is OI the minimum oxygen content in a mixture with nitrogen, at a stable combustion of a test specimen is observed.)

For the chemical modification of Polystyrene is styrene containing chlorine, bromine or phosphorus Monomers copolymerized, namely Vinyl chloride, vinyl bromide, vinylidene chloride, chlorinated and brominated Styrenes, halogens containing acrylates, halogenated fumarates, N-phenylmaleimides, phosphorylated styrene, halogenated vinyl and Allylphosphonsäureestern, Phenyldichlorophosphine and tris (methacryloylbromethyl) phosphate (Low Combustibility Polymer Materials, ed. A.N. Pravednikov, Moscow, Khimiya, 1986, P. 132).

With the method of chemical modification of carbon chain polymers for fireproofing purposes you get a fire protection effect against various treatments resistant is. However, this requires changes of polymer manufacturing technology and leads to the appearance of a number negative properties in the final product, what the application possibilities for this Method restricted.

Methods of chemical are on the scale of use Modification far behind the method of incorporating flame retardants and flame retardant systems in the polymer processing stage (Berlin A.A., Volfson S.A., Oshmyan V.G. et al., Principles of Creation of Fireproofed Polymer Materials, Moscow, Khimiya, 1990, p. 240).

The process of making flame retardant synthetic materials by incorporation of Flame retardant in the polymer melt during the shaping enables Preservation of the existing technology for processing objects very economical and creates conditions for ecological development safe procedure. It also ensures that the fire resistant equipment is highly resistant to wet treatments.

The most used flame retardants for rubbers are aluminum trihydroxide and aluminum oxide, which are not just flammability of the rubber, but also the disadvantage of flue gas emissions turn off.

To prepare compositions that The degree of filling of the polymer composition must not assist combustion in air with flame retardant be at least 50% what the procedure complicated to treat the compositions and the physical and mechanical indicators (Low Combustility Polymer Materials, ed. A.N. Pravednikov, Moscow, Khimiya, 1986, p. 132).

It is also known to use Al (OH) ₃ and Mg (OH) ₂ in combination with expanded graphite (Khokhlova LA, Aseyeva RP, Ruban LV, International Conference on Low Combustibility Polymer Materials, Alma Ata, 1990, Volume 1, p. 16-18).

A big problem in processing of inert flame retardants consists in the migration of (with incompatible with the polymer lattice) Additives from the polymer grid on its surface, because these additives are not are bound to it. this leads to a reduction in the fire protection effect and increased in contact with the surface of metals the corrosion activity with the surface of the Metals.

More effective flame retardants for polyolefins and synthetic rubbers are organic bromine flame retardants that are incorporated into polymers in combination with the synergistic additive antimony trioxide ( US 5116898 , MPC C 08K 5/06). The flame retardant content can be reduced by replacing part of the trioxide. To reduce the flammability of polystyrene, halogenated aliphatic compounds are used in combination with antimony trioxide: chlorinated paraffins, perchlorinated alkanes C ₂ Cl ₆ , C ₄ Cl ₁₀ , bromine-containing aliphatic compounds (tetrabromethane, tetrabromoctane, 1,2,3,4-tetrabromo-2 , 3-dimethylbutane, 2,3,4,5-tetrabromo-2,5-dimethylhexane and others) (Low Combustibility Polymer Materials, ed. AN Pravednikov, Moscow, Khimiya, 1986, p. 132).

To self-extinguishing polyolefins and synthetic rubbers To give properties high concentration of organic flame retardants (up to 40% Chlorine or 20-30% Bromine) can be used.

In various publications will use red phosphorus (the polymeric form of the elementary Phosphors) as flame retardants for polyolefins (Low Combustibility Polymer Materials, ed. A.N. Pravednikov, Moscow, Khimiya, 1986, p. 132). Has a polyethylene with an OI of 26.2% a phosphorus content of 8%. When processing red phosphorus containing polyolefins, however, becomes toxic phosphorus (Phosphine) emitted.

The use of ammonium polyphosphates as a flame retardant for Polyolefins and synthetic rubbers are known (UK patent application 2272444, MPC C 08F 8/40, C08F 9/44).

The effectiveness of ammonium polyphosphates depends on it how finely they are crushed. Even with a very fine degree of dispersion however, to achieve an OI of 28%, a high degree of filling (40-50% by weight) required, resulting in a substantial Reduction of the physical and mechanical properties of the Leads.

Numerous investigations have been carried out the synthesis of amides or alkylamides of phosphoric acid or alkylphosphonic and their use as flame retardants for fireproofing Dedicated to polymer materials. From studies by Drews (Drews M.J., Textilveredlung, 1973, Volume 8, pp. 180-186) showed that connections with a P-N bond represent more effective flame retardants than Connections with P-O bonds. The synthesis of phosphorus triamide has already been described (Herlinger H., Textilveredlung, 1977, volume 12, pp. 13-20), and it is proposed to use it for fireproofing To use cellulose materials. The reaction was accomplished by implementing Phosphorsäuretrichloranhydrid performed with ammonia in chloroform at a temperature of 10 ° C. On The problem with the flame retardant thus obtained is that it is reduced of the physical and mechanical indicators of the modified Polymer materials by 50-60%.

To solve this problem has been through Treatment of phosphorus oxychloride with dimethylamine and methylamine Pentamethylphosphorsäuretriamid (L. Blanc R.B., Text. Chem. Colorist, 1975, Volume 7, No. 10, pp. 23-25). However, the synthesized compounds had high heat resistance and were therefore less of a fire retardant for polymer materials effective.

In another work a Process for the synthesis of methylphosphonic acid diamide by treatment of methylphosphonic dichloroanhydride with liquid Ammonia in chloroform medium proposed (Ratz R.J., J. Am. Chem. Soc., 1955, volume 77, pp. 4170-4171). All reagents included of the solvent were anhydrous. As this work showed, methylphosphonic acid diamide, that when cooking in a medium of diethylamine and chloroform separates from the reaction mixture, a low resistance across from hydrolyzing agents and goes even under the action the moisture in the air gradually into the ammonia salt Methylphosphonic acid via. by virtue of this problem cannot use this compound as a flame retardant for incorporation into molten Polymer are recommended.

To eliminate this disadvantage proposed in RU-PS 20993384, partially hydrolyzed methylphosphonic acid diamide - the ammonia salt of Methylphosphonic acid diamide - in one heat-resistant cover Base of polyaramides to microencapsules. The flame retardant produced however assigns one for Polyolefins have insufficient fire protection and can only be used for Reduction in flammability of polyamides and polyesters recommended become. It should be noted that the procedure is difficult the microencapsulation in polyaramide casings without structural defects.

The use of organosilicon compounds to modify flame retardants and to facilitate the processing of hochge filled compositions is known. To facilitate processing, modifying additives are incorporated into the compositions: e.g. B. there is a known flame-retardant composition (Bolikhova VD, Drobinin AN, Plastic Masses, Moscow, Z.-S. 1994, pp. 46-51), the antipyrene Al (OH) ₃ and as a modifying additive silica and Contain polysilicic acids.

Halogens containing organic compounds are used to modify hetero chain polymers, especially polyesters. These are mainly aromatic flame retardants containing bromine. They are used because of their higher heat resistance and less smoke generation compared to halogens containing aliphatic compounds (Namets RC, Plastics Compounding, 1984, Volume 7, No. 4, pp. 26-39). Special additives are used to reduce the development of flue gas when flame retardants containing halogens are incorporated. The most effective of these additives are the oxides of aluminum, zinc and tin (Cusack PA, Fire and Mater., 1986, Volume 1, No. 1, pp. 41-46).

Are problematic in use of flame retardants containing halogens the low resistance of the manufactured materials against the influence of ultraviolet Radiation, its high toxicity and the corrosion of the equipment during processing.

The disadvantages listed above apply to phosphorus bisphenol Flame retardants containing S mostly not too (Horrocks A.P., Polym. Degrad. Stab., 1996, volume 54, pp. 143-154). The commercial company Albright and Wilson sells a cyclic Phosphonate with the designation Amgard 1045 (GB patent application 2250291, MPC C08K 8/03, 7/04).

Incorporation of red phosphorus (1-15% by weight) and melamine cyanurate (4-15% by weight) in a polyester allows the manufacture of a high strength material (GB patent application 2250291, MPC C08K 8/03, 7/04). The application procedure described there red phosphorus, which has a high risk of fire, is quite complex. Moreover discolour the polyester compositions produced to some extent.

The company Hoechst (Germany) provides fire-protected polyester fibers using a phosphorus-containing bifunctional compound as a flame retardant. This connection is called Trevira FR and CS distributed (Baranova T.L., Smirnova T.V., Ayzenshteyn E.M., Fireproofed Polyester Fibers, Information Review, Series Chemical Fiber Industry, Moscow, NIITEKhIM, 1986, p. 42). The fire protection properties however, these fibers are not good enough and for a phosphorus content of 0.8-1.0 % By weight the OI is 26-27%.

It has undergone intensive development in recent years the tendency to incorporate antipyrene additives in polymer compositions in the form of microcapsules.

Microencapsulation methods are for tetrafluorodibromoethane (Boiling point 47.5 ° C) and tetrachlorodifluoroethane (boiling point 92.8 ° C) have been developed. For the bowl gelatin and gum arabic are used. The Italian company Eurand has the technical production of microencapsulated tetrafluorodibromethane (Freon - 114 B2) organized (Aleksandrov L.V, Smirnova T.V., Khalturinskiy N.A., Fireproofed Materials, Moscow, VNIIPI, 1991, p. 89).

There are known fire protection compositions in which the antipyrene is enclosed in a polymer shell, e.g. B. a composition based on polyolefins which contains Al (OH) ₃ encapsulated as a flame retardant in a polyurethane shell (EP A 0411971 B1, C 08 K 9/08, 1995), or a composition containing microencapsulated Tris (2,3 -dibromopropyl) phosphate in a shell made of polyvinyl alcohol or urea-formaldehyde resin ( US 3660821 , cl. 260-2.5, 1972).

The problem with the known Polymer compositions with microencapsulated flame retardant the high level of flame retardant (up to 60%) of low physical and mechanical indicators leads.

Yet another major problem with the known compositions is that it is impossible to process them at T> 200 ° C (ie they cannot be molded) since Al (OH) _{3 is} degraded at T> 180 ° C and the polymer shells of the microencapsulated flame retardants in the known compositions begin to degrade at 160-190 ° C, which leads to the release of the antipyrene from the shell and its decomposition, which reduces the fire resistance of the compositions and the compositions are more difficult to process.

There is a known polymer composition based on polyolefins microencapsulated in melamine-formaldehyde resin contains red phosphorus (EP A 0250662, MPC C 08 K 9/10, 1986). Melamine-formaldehyde resin is somewhat more stable than the antipyrene shell in the other known ones Compositions, but it starts at T> 200-220 ° C also decompose, followed by hydrolysis of the red one Phosphorus and the formation of highly toxic phosphines. Hence acts it is also a composition that is not processed by molding can be because this happens at too high temperatures (250-280 ° C).

Object of the invention

Despite the variety of methods proposed to reduce the flammability of polymer materials, the problem of manufacturing flame retardants for polymer materials and more effective agents for the production of flame-retardant polymer compositions. The present invention is primarily aimed at solving this problem.

• – Verringerung des Rauchgasbildungsvermögens bei der Pyrolyse und Verbrennung von brandgeschützten Polymerzusammensetzungen;
• – Verbesserung der Bearbeitbarkeit von Polymerzusammensetzungen;
• – Ermöglichung der Implementierung der entwickelten Verfahren unter Verwendung von bereits in Produktionslinien für die Behandlung von Polyolefinen und Synthesekautschuken installierten Einrichtungen.

Other problems that the invention addresses are:

• - Reduction of the smoke generation capacity during the pyrolysis and combustion of fire-protected polymer compositions;
• - Improving the machinability of polymer compositions;
• - Enabling the implementation of the developed processes using equipment already installed in production lines for the treatment of polyolefins and synthetic rubbers.

The authors of the present invention previously used the microencapsulated antipyrene T-2 as a flame retardant for Polyethylene and polypropylene proposed (Zubkova N.S. et al., Plastmassy, 1996, No. 5, pp. 35-36). This is a technical mixture of two individual compounds - the ammonium salt of methylphosphonic acid and ammonium chloride.

The authors later discovered to her surprise that a Complex compound from the ammonia salt of methylphosphonic acid amide and ammonium chloride provides more effective fire protection than that Technical mixture mentioned above. In the absence of a theory to justify this unexpected result, it can be assumed that complex compounds more active catalysts for which represent coke formation processes for reducing combustibility of polymer materials are responsible.

worin R für einen C_1-3-Alkylrest steht, vorschlagen.The invention thus relates primarily to the production of a new flame retardant for polymer compositions for which we have complex compounds from the ammonia salt of an alkylphosphonic acid amide and ammonium chloride of the formula (I)

where R is a C _1-3 alkyl radical, suggest.

It was determined experimentally that in this complex compound about 1.8 molecules of ammonium chloride per molecule of ammonia salt of the alkylphosphonic acid amide available.

To produce the new complex compound according to formula (I) one can alkylphosphonic dichloroanhydride in an organic solvent medium at one temperature from 10–20 ° C with gaseous ammonia implement.

The flame retardant that the object The present invention forms can by various methods be used.

To provide improved Fire protection properties of such polymers as polyethylene, Polypropylene and the copolymers of various based on it The flame retardant produced should be in the compositions Polymer processing stage are incorporated.

For example, you can use the new flame retardant co-extrude with the polymer and then shape the polymer fiber and process it back into granules.

Another claimed Process for the preparation of polymer materials of the above type the new flame retardant is mixed with the polymer composition, after which the mass is rolled and pressed into objects.

For the methods described above and others are there to manufacture of low fire risk polymer materials Incorporation of the flame retardant developed by the authors Recommended in the course of its processing in the polymer, initially that Flame retardant microencapsulated in a polymer shell, where the capsule size 5 to Is 25 μm. For the production the microcapsule shell can be polyethylene or polyorganosiloxanes, especially polyvinylmethyldiethoxysiloxane or use polyaminopropylethoxysiloxane. For production of low fire risk polymer materials such as polyester and epoxy resins, that must new flame retardants incorporated into the polymer composition before it becomes firm.

These compositions can be widely used as a binder for Glass plastics, sealants, cast insulation and adhesives, as protective covers for various Materials and for making objects by casting in many technical fields, such as B in electrical engineering and electronics, and also in construction, aviation, shipbuilding, etc.

It is in a solid state in the compositions produced around solid impenetrable Materials that are not soluble in organic solvents, across from the action of acids and bases resistant are, good thermal properties, physical properties, mechanical properties and electrical insulation ungseigenschaften have no volatile Contain components and extinguish when discharged from a flame.

The new flame retardant can too for the production of synthetic rubbers with a low fire risk used to advertise.

• – ist der Sauerstoffindex OI der Sauerstoffmindestgehalt in einem Gemisch mit Stickstoff, bei dem eine stabile Verbrennung eines Probekörpers nach Entfernung der Zündquelle beibehalten wird;
• – ist die Nachbrennzeit die Verbrennungszeit des Probekörpers nach Entfernung der Zündquelle;
• – ist die Flammwidrigkeitsklasse PV eine Note von 0 bis 4, die gemäß GOST 28157–89, einer Norm der ehemaligen UdSSR, bestimmt wurde.

The invention will now be further explained on the basis of exemplary embodiments. In this example len:

• - the oxygen index OI is the minimum oxygen content in a mixture with nitrogen, in which a stable combustion of a test specimen is maintained after removal of the ignition source;
• - the afterburn time is the burn time of the test specimen after removal of the ignition source;
• - the flame retardancy class PV is a grade from 0 to 4, which was determined according to GOST 28157–89, a norm of the former USSR.

Examples of the execution of the Invention Example 1. Preparation of the complex compound.

300 ml of chloroform are saturated with gaseous ammonia at a temperature of 10 ° C. A solution of methylphosphonic acid dichloroanhydride (60 g methylphosphonic acid dichloroanhydride in solution in 200 ml chloroform) is slowly added to the solution obtained over a period of two hours. Ammonia is continuously blown through the solution to maintain the alkaline medium (pH = 9). The temperature of the process should not exceed 20 ° C. The sediment that forms is filtered off on a Büchner funnel and dried in a vacuum cabinet. The yield of the synthesized product is 78.9%. The empirical formula is CH _16.3 PN _3.8 O ₂ Cl _1.8 .

Elemental analysis: Found: C 5.8, H 8.1, P 14.3, N 24.9, Cl 30.7; Calculated: C 5.8, H 7.8, P 14.9, N 25.5, Cl 30.6.

The formation of the complex compound was performed using thermogravimetric analysis (TGA), differential calorimetry (DSC) and X-ray photoelectron spectroscopy (RPES) proven.

The TGA curve of the complex compound from the ammonia salt of metaphosphonic acid amide and ammonium chloride contains a thermal oxidation decomposition peak in the temperature range of 240-400 ° C with a Maximum at 348 ° C, that for the single connection is characteristic. The DSC data show that this synthesized product at a temperature of 202 ° C (one peak), the much higher is the melting point of the pure ammonia salt of methylphosphonic acid amide (124 ° C), melts.

The RPES spectrum of the synthesized product shows an unusually low binding energy of the 2p electrons of the chlorine level (198.1 eV), which indicates the formation of the complex compound. The N1 _S spectrum contains two main peaks - at a binding energy of 400.2 eV, corresponding to the PN bonds, and at a binding energy of 401.7 eV, corresponding to the nitrogen in ammonia form, which is considerably lower than the nitrogen bond in NH ₄ Cl.

Example 2.

A composition of 75 g polypropylene crumbs and 25 g of flame retardant according to the invention are fed into a screw extruder. The shaping takes place at 170 ° C. The homogeneous melt enters a water bath (18-25 ° C) and becomes the granulation fed. The modified polyethylene has an OI of 27.6, no afterburn time, flame resistance class PV-0 according to the USSR standard (GOST 28157-89).

Example 3.

A composition of 75 g polypropylene crumbs and 25 g of the invention, in a polyethylene cover (containing 10 wt .-% flame retardant, microcapsule size 25 μm) encapsulated flame retardant is processed analogously to Example 1. Molding temperature 230 ° C. The modified polypropylene has an OI of 28.2, no afterburn time and the flame retardancy class PV 0th

Example 4.

A composition of 90 g polyester crumbs and 10 g of the invention, in an envelope (containing 5% by weight flame retardant, microcapsule size 10 μm) microencapsulated flame retardant is processed analogously to Example 1. Molding temperature ~ 270 ° C. The modified Polyester has an OI of 29.6%, no afterburn time and the flame resistance class PV 0th

Example 5.

A composition of 85 g polyester crumbs and 15 g of the invention, in an ethylene shell (containing 2% by weight of flame retardant, microcapsule size 10 μm) microencapsulated flame retardant is processed analogously to Example 1. Molding temperature 270 ° C. The modified polyester has an OI of 31.0, no afterburn time and the flame retardancy class PV 0th

Example 6.

100 g epoxy resin with 10 g Harder and 15 g of flame retardant according to the invention mixed and allowed to solidify at room temperature for 48 hours; the solid composition thus modified becomes a flame-retardant Material. The OI (oxygen index) is 35, the afterburn time is is zero and the flame resistance class is PV-0.

Example 7.

Glass fiber is saturated with an epoxy composition prepared according to Example 5 and allowed to solidify at a temperature of 60-80 ° C for 20-30 minutes. The composition obtained contains 40% by weight of binder (epoxy together composition) and 60 wt .-% filler (glass fiber). The composite material is flame-retardant and has no afterburn time and flame retardancy class PV-0.

Example 8.

A composition of 60 g unsaturated polyester resin, 15 g according to the invention, in a polyaminopropylethoxysiloxane shell (containing 5 wt .-% flame retardant, microcapsule size 15 μm) microencapsulated flame retardant and 25 g staple fiber (viscose, polycaproamide) was at a temperature of 180 ° C and a pressure of 80 kg / cm ² pressed. The plastics obtained have an OI of 29.5% and no afterburn time.

Example 9.

A composition of 80 g rubber mixture with butadiene-styrene rubber and 20 g of flame retardant according to the invention will be thorough mixed, rolled at a temperature of 140-150 ° C and then at a Temperature of 170-180 ° C pressed to objects. The modified rubber compound has an OI of 28% and no afterburn time.

Example 10.

A composition of 85 g rubber mixture based on isoprene rubber and 15 g of the invention, in a polyaminoethoxysiloxane shell (containing 5% by weight of flame retardant, microcapsule size 15 μm) microencapsulated flame retardant is processed analogously to Example 5. The modified rubber compound has an OI of 28.1 and no afterburn time.

Example 11.

A composition of 80 g polymethyl methacrylate and 20 g of flame retardant according to the invention is processed analogously to example 1 at a temperature of 220 ° C. The modified polymethyl methacrylate has an OI of 27.2 and no afterburn time.

Example 12.

A composition of 75 g polycaproamide (PCA) and 25 g of the invention, in an ethylene shell (containing 10% by weight of flame retardant, microcapsule size 25 μm) microencapsulated flame retardant is processed analogously to Example 1. Molding temperature 230 ° C. The modified PCA has an OI of 29%, no afterburn time and the flame retardancy class PV 0th

Example 13 (for comparison)

A composition of 85 g polyester crumbs and 15 g of a technical mixture of 7.7 g of ammonia salt of methylphosphonamide and 7.3 g of ammonium chloride are processed as in Example 4. The modified Polyester has an OI of 27.6%.

Example 14 (for comparison)

A composition of 75 g polypropylene crumbs and 25 g of an industrial mixture of 12.8 g of ammonia salt of methylphosphonic acid amide and 12.2 g of ammonium chloride are processed as in Example 3. The modified polyester has an OI of 24.8 and flame retardancy class PV-1.

Example 15 (for comparison)

A composition of 75 g polyethylene crumbs and 25 g of an industrial mixture of 12.8 g of ammonia salt of methylphosphonic acid amide and 12.2 g of ammonium chloride are processed as in Example 2. The modified polyester has an OI of 24.8 and flame retardancy class PV-1.

Example 16 (for comparison)

A composition of 75 g polycaproamide crumbs and 25 g of an industrial mixture of 12.8 g of ammonia salt of methylphosphonic acid amide and 12.2 g of ammonium chloride are processed as in Example 12. The modified polyester has an OI of 24.8 and flame resistance class PV-1.

As the comparative examples show, the proposed complex compound is a more effective antipyrene for Polyethylene (Examples 2-15), Polypropylene (Examples 3-14), Polyester (Examples 5-13) and polymers other than a technical mixture of the two Compounds of ammonia salt of methylphosphonic acid diamide and ammonium chloride.

Furthermore, the diamide has a low one resistance across from the action of hydrolyzing agents, and even under The action of moisture in the air affects methylphosphonic acid diamide gradually about that Ammonia salt into the methylphosphonic acid.

Therefore, the use of the proposed Complex a qualitatively new solution the problem of reducing the flammability of polymer materials represents.

Claims (35)

Complex compound from the ammonia salt of an alkylphosphonic acid amide and ammonium chloride of the formula (I)

wherein R is a C _1-3 alkyl radical. A complex compound according to claim 1, in which about 1.8 molecules of ammonium chloride per molecule of ammonia salt of the alkylphosphonic acid amide available. Process for the preparation of a complex compound from the ammonia salt of an alkylphosphonic acid amide and ammonium chloride of the formula (I), in which alkylphosphonic dichloroanhydride is used in an organic solvent medium at a temperature of 10-20 ° C with gaseous ammonia implements. Flame retardant for polymer materials, consisting of a complex compound from the ammonia salt of an alkylphosphonic acid amide and ammonium chloride of the formula (I)

wherein R is a C _1-3 alkyl radical. A flame retardant according to claim 4, in which about 1.8 molecules of ammonium chloride per molecule of ammonia salt of the alkylphosphonic acid amide available. Flame retardant according to claim 4 or 5, characterized in that it in a polymer sleeve is microencapsulated. Flame retardant according to claim 6, characterized in that the polymer casing There is polyethylene. Flame retardant according to claim 6, characterized in that the polymer casing Polyorganosiloxanes exist. Flame retardant according to claim 8, characterized in that the polyorganosiloxanes from the group consisting of polyvinyldimethyldiethoxysiloxane and Polyaminopropylethoxysiloxane originate. Process for the production of low fire risk Polymer materials by incorporating the flame retardant in the polymer during its processing, characterized in that as Flame retardant is a complex compound from the ammonia salt alkylphosphonic acid and ammonium chloride of formula (I) used. Process for the production of low fire risk Polymer materials according to claim 10, characterized in that the series to: - the Flame retardant co-extruded with the polymer; - the polymer fiber shapes and - granulated. Process for the production of low fire risk Polymer materials according to claim 10, characterized in that the series to: - the Flame retardant mixes with the polymer composition; - the mass rolls and - too objects pressed. Method according to one of claims 10-12, characterized in that that he the flame retardant first in a polymer sleeve microencapsulated. A method according to claim 13, characterized in that the microcapsules 5–25 μm in size. A method according to claim 13, characterized in that the polymer casing There is polyethylene and 10-15 Wt .-% contains flame retardant. Process according to Claim 13, characterized in that polyorganosiloxanes are used for the polymer shell used. A method according to claim 16, characterized in that the polyorganosiloxane consists of polymethyldiethoxysiloxanes and the shell 2-5 wt .-% Contains flame retardants. A method according to claim 16, characterized in that as Polyorganosiloxane Polyaminopropylethoxysiloxan used and the Shell 2–5% by weight Contains flame retardants. Method according to one of claims 10-18, characterized in that he Polyethylene, polypropylene and copolymers of various based on it Compositions processed. Method according to one of claims 10-18, characterized in that he Polystyrene and copolymers of various compositions based thereon processed. Process for the production of low fire risk Polymer materials by incorporating the flame retardant in the polymer, characterized in that it is used as a flame retardant a complex compound from the ammonia salt of an alkylphosphonic acid amide and ammonium chloride of formula (I) used in the polymer composition is incorporated before it becomes firm. A method according to claim 21, characterized in that in addition to a filler to the flame retardant incorporated into the polymer composition and as a result of the saturation of the filler with the solidifying polymer composition a low fire risk containing materials. Method according to one of claims 21 to 22, characterized in that that he Processed polyester. Method according to one of claims 21 to 22, characterized in that that he Processed epoxy resins. Process for the production of low fire risk Polymer materials, characterized in that a complex compound from the ammonia salt of an alkylphosphonic acid amide and ammonium chloride of formula (I) in a synthetic rubber containing polymer composition incorporated, which was then rolled and subsequently became an object pressed becomes. Low fire risk polyethylene, manufactured by a method according to any one of claims 10 to 18. Low fire risk polypropylene by a method according to any one of claims 10 to 18. Low fire risk polystyrene manufactured by a method according to any one of claims 10 to 18. Low fire risk copolymers based on Polyethylene, polypropylene and polystyrene manufactured according to a Method according to one of the claims 10 to 18. Low fire risk polyester manufactured according to a procedure. Claim 21. Low fire risk epoxy resins manufactured by a method according to claim 21. Low fire risk composite materials by a method according to claim 22. Synthetic rubbers with a low fire risk, manufactured by a method according to claim 25. Low fire risk polycaproamide materials, produced by a method according to claim 13. Low fire risk polymethyl methacrylate compositions, produced by a method according to claim 11.